CN110040726A - A method of preparing large-area high-quality uniformly a small number of layer graphene films - Google Patents
A method of preparing large-area high-quality uniformly a small number of layer graphene films Download PDFInfo
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Abstract
The present invention relates to graphene new material and its chemical vapor deposition (CVD) preparation field, specially a kind of method for preparing the uniform a small number of layer graphene films of large-area high-quality, suitable for preparing the graphene film of the uniform number of plies of large-area high-quality.Using corronil as growth substrate, the graphene film of the uniform number of plies of large-area high-quality is prepared by chemical vapour deposition technique, it is subsequent to obtain high quality uniformly a small number of layer graphene films with the method for being bubbled transfer.The present invention has short preparation period, simple process, production cost is low, Product size and thickness are easy to regulate and control and be suitable for the features such as large area preparation, for large-area high-quality, uniformly a small number of layer graphene film scene effect transistors, transparent conductive film, the research and application in the fields such as flexible electronic device lay the foundation.
Description
Technical field:
The present invention relates to graphene new material and its chemical vapor deposition (CVD) preparation fields, specially a kind of to prepare greatly
The method of the uniform a small number of layer graphene film of area and high quality, the graphene suitable for preparing the uniform number of plies of large-area high-quality are thin
Film.
Background technique:
Graphene is a kind of by the closelypacked new carbon with bi-dimensional cellular shape crystal structure of single layer of carbon atom.
It is also other dimension carbon materials of composition simultaneously, such as: the basic structural unit of carbon pipe, fullerene, graphite etc..Because it is unique
Crystal structure so that graphene have very excellent photoelectric properties.For example, the room temperature carrier mobility of graphene can be with
Up to 105cm2v-1s-1, it is more than 100 times of common silicon materials in semi-conductor industry.Its conductivity is up to 106S/m, surface resistance
About 30 Ω/ are the materials that electric conductivity is best at room temperature.The thickness (0.335 nanometer) of the special single layer of carbon atom of graphene
It is set only to absorb 2.3% visible light, i.e. single layer light transmittance is 97.7%.Therefore, graphene in flexible electronic device, transparent lead
The fields such as conductive film, solar battery have broad application prospects.
After graphene is found for the first time, although different layers of high quality graphite can be obtained with the method for mechanical stripping
Alkene, but due to the sample of acquisition is size-constrained and repeatable difference etc., can not be promoted in actual production.2009
Year, scientists prepare multi-layer graphene using chemical vapour deposition technique (CVD) in nickel substrate.And chemical vapour deposition technique
With at low cost, favorable repeatability, can widely be studied from this large area the characteristics of preparing graphene.The most commonly used two kinds
Typical metallic substrates are copper and mickel.Graphene is made to show surface catalysis on its surface since the molten carbon amounts of copper is very low
Growth mechanism, therefore relatively uniform single-layer graphene is easy to get on copper surface.And the molten carbon amounts of nickel makes greatly graphite very much
The growth of alkene shows the growth mechanism of solution modeling, therefore can obtain the number of plies and the uncontrollable multilayer of uniformity on the surface of nickel
Graphene film.And corronil in summary advantage of two kinds of metals in terms of growing graphene, it is expected to obtain large area high
Uniform quality minority layer graphene film, widens graphene in the application prospect of photoelectric field.Meanwhile utilizing the side for being bubbled transfer
Method is used repeatedly alloy substrates, and etching method is avoided to further decrease experimental cost to the waste of metallic substrates, be
The industrialized production of the uniform a small number of layer graphene of large-area high-quality provides possibility.
Summary of the invention:
The purpose of the present invention is to provide a kind of method for preparing the uniform a small number of layer graphene film of large-area high-quality, solutions
The problems such as certainly quality of materials obtained in research is poor at present, the number of plies is uneven, and the number of plies is difficult to control, for the sheet for studying graphene film
Intrinsic characteristics lays the foundation with its application is explored.
The technical scheme is that
A method of large-area high-quality uniformly a small number of layer graphene films being prepared, using corronil as growth base
Bottom prepares the graphene film of the uniform number of plies of large-area high-quality, subsequent bubbling transfer by chemical vapour deposition technique
Method obtain high quality uniformly a small number of layer graphene film.
The described method for preparing the uniform a small number of layer graphene films of large-area high-quality, the specific steps are as follows:
(1) the growth preparation of the uniform a small number of layer graphene film of large-area high-quality: in chemical vapor deposition processes, with
Corronil is as growth substrate, and in conjunction with the advantage of two kinds of metal growth graphenes of copper and mickel, and then it is high-quality to prepare large area
The uniform a small number of layer graphene films of amount；
(2) coating of high molecular polymer protective layer: the uniform number of plies of high quality graphene film uniformly
One layer of high molecular polymer is coated as protective layer, prevents graphene film from destroying in subsequent processes；
(3) it is bubbled transfer method: graphene film is transferred to other substrates from corronil substrate, shifted using being bubbled
Method corronil substrate is separated in the electrolytic solution with graphene, obtain high molecular polymer/graphene film and answer
Close film and corronil substrate Reusability；
(4) removal of high molecular polymer protective layer: obtained high molecular polymer/graphene film composite membrane is placed
In target substrate, the high molecular polymer protective film dissolution removal on graphene film surface will be covered on organic solvent.
The described method for preparing the uniform a small number of layer graphene films of large-area high-quality, the corronil substrate of use are thick
Degree is 1 μm~200 μm, and purity is 98wt%~99.9999wt%, and the content of nickel is 1wt%~50wt% in alloy.
The described method for preparing the uniform a small number of layer graphene films of large-area high-quality, chemical vapour deposition reaction process
In, carbon source is hydrocarbon: methane, ethane, ethylene, acetylene, benzene, toluene, hexamethylene, ethyl alcohol, methanol, acetone, an oxidation
The one or more of carbon；Alternatively, carbon source is solid carbon source: the one or two of amorphous carbon, paraffin, high molecular polymer
More than, high molecular polymer is polymethyl methacrylate, polycarbonate, polystyrene, polyethylene, one kind of polypropylene or two
Kind or more.
The described method for preparing the uniform a small number of layer graphene films of large-area high-quality, chemical vapour deposition reaction process
In, carrier gas is hydrogen or carrier gas is the mixed gas of hydrogen and inert gas.
The described method for preparing the uniform a small number of layer graphene films of large-area high-quality, chemical vapor deposition growth graphite
The temperature of alkene is 900 DEG C~1300 DEG C, and growth time is 1~300 minute.
The described method for preparing the uniform a small number of layer graphene films of large-area high-quality, the electrolyte for being bubbled transfer were
Sodium hydrate aqueous solution or potassium hydroxide aqueous solution, the electric current for being bubbled transfer is 0.1A~5A.
The described method for preparing the uniform a small number of layer graphene films of large-area high-quality, using high molecular polymer conduct
The protective layer of the uniform a small number of layer graphene film of high quality, to graphene film is transferred on other matrixes, polyphosphazene polymer
Conjunction object is the one or more of polymethyl methacrylate, polyethylene, polystyrene, polypropylene.
The described method for preparing the uniform a small number of layer graphene films of large-area high-quality, by graphene and corronil base
After the separation of bottom, high molecular polymer protective layer is removed with organic solvent, the organic solvent used is ketone, halogenated hydrocarbons, aromatic hydrocarbons
The one or more of reagent.
The described method for preparing the uniform a small number of layer graphene films of large-area high-quality, uniform number of plies graphene film layer
Number is 3~10 layers, every layer of graphene film with a thickness of 0.3~0.8nm, the number of plies depends on the supply of carbon source amount, growth time
And the access times of corronil substrate, size depend on the size of metallic matrix used in preparation process, entire material
Expect that uniform component, thickness are controllable, for light transmittance 85% or more, square resistance is the Ω of 10 Ω~1000.
The invention has the advantages and beneficial effects that:
1. the present invention combines graphene the advantages of growing on metal copper and mickel, propose a kind of to prepare big face with corronil
The method of the uniform a small number of layer graphene film of product high quality.In conjunction with the method for being bubbled transfer, so that alloying metal substrate is able to instead
It is multiple to utilize, so that preparation cost is reduced, and the same substrate for using different numbers, the repeatability of graphene growth
It is good.
2. the graphene film that the present invention obtains has good number of plies controllability, and the number of plies is more uniform.Also,
The crystalline quality of graphene film is very high, therefore also has excellent photoelectric properties, high visible light permeability, lower electricity
Resistance, these features are the uniform graphene film scene effect transistor of the high quality number of plies, transparent conductive film, flexible electronic device
The research such as part and application lay the foundation.
3. CVD method proposed by the present invention can carry out under normal pressure, have it is easy to operate, be easy to regulate and control and be easy to large area
The features such as preparation, the areal extent of graphene film depend on reaction cavity size, and the area of graphene film can reach 10 ×
12cm2More than.
4. the uniform number of plies graphene film number of plies of the high quality that the present invention obtains is 3~10 layers, the number of plies is supplied depending on carbon source
The amount given, growth time and alloy access times etc., size depend on the size of metallic matrix used in preparation process,
Entire material composition is uniform, thickness is controllable, and light transmittance reaches as high as 93%, and square resistance is the Ω of 10 Ω~1000.
Detailed description of the invention:
Fig. 1, the experimental provision schematic diagram of the uniform a small number of layer graphene film of CVD method growing large-area high quality.In figure, 1
Gas access；2 metallic substrates；3 gas vents；4 heating furnaces.
Fig. 2, the optical photograph and scanned photograph of different number of plies graphene films.Wherein, a, e are respectively three layers of graphene
Optical photograph and scanned photograph, b, f are respectively the optical photograph and scanned photograph of four layers of graphene, and c, g are respectively five layers of graphite
The optical photograph and scanned photograph of alkene, d, h are respectively the optical photograph and scanned photograph of six layers of graphene.
Fig. 3, the uniform five layers of graphene film Raman spectrum of large area.Wherein, abscissa Raman Shift represents Raman peaks
Position (cm-1), ordinate Intensity represents relative intensity (a.u.).
Fig. 4, various sizes of uniform five layers of graphene/PET film photomacrograph.Wherein, 5 × 6cm of (a) area2, (b)
10 × 12cm of area2。
Fig. 5, the uniform graphene film light transmittance of different layers of large area and resistivity contrasts.Wherein, (a) present invention three
To the light transmittance of six layers of graphene film, abscissa Wavelength is represented wavelength (nm), and ordinate Transmittance is represented
Light transmittance (%)；(b) the resistivity statistical chart of three to six layers of graphene film of the invention, Counts represent statistical magnitude, Layer
Number represents the number of plies, and Sheet Resistance represents square resistance (Ω per square).
Fig. 6 uses the pattern for the graphene film that the identical corronil substrate grown of different numbers goes out.Wherein, 1 (a)
It is secondary；(b) 2 times；(c) 3 times；(d) 4 times.
Specific embodiment:
In the specific implementation process, the method that the present invention prepares the uniform a small number of layer graphene film of large-area high-quality, is adopted
Corronil is used as growing substrate, prepares the graphene film of the uniform a small number of layers of large-area high-quality, subsequent bubblings shifts
Method obtains the uniform graphene film of the number of plies of high quality.
Specific step is as follows for this method:
(1) the growth preparation of the uniform a small number of layer graphene film of large-area high-quality: using corronil as growth substrate,
It can (the molten carbon amounts of copper be lower, is easy to grow the number of plies more uniform in conjunction with the advantage of copper and mickel two kinds of metals growth graphene
Single-layer graphene film, and the molten carbon amounts of nickel is very high, is easy to grow the uncontrollable graphene film of the number of plies), and then prepare
The uniform a small number of layer graphene film of large-area high-quality.
Used metallic substrates are corronil, and for the alloy of use with a thickness of 1 μm~200 μm, preferred scope is 100 μm
~200 μm；Purity is 98wt%~99.9999wt%, and preferential range is 99.5%~99.9999%；The content of nickel in alloy
For 1wt%~50wt%, preferred scope is 10wt%~30wt%.Used CVD cracking carbon source is hydrocarbon: first
The one or more of alkane, ethane, ethylene, acetylene, benzene, toluene, hexamethylene and ethyl alcohol, methanol, acetone, carbon monoxide；
Alternatively, CVD cracking carbon source is solid carbon source amorphous carbon, paraffin or polymethyl methacrylate (PMMA), polycarbonate, polyphenyl
One of high molecular polymers such as ethylene, polyethylene, polypropylene kind or two or more.The carrier gas that CVD growth uses is hydrogen, or
Carrier gas is the mixed gas of hydrogen and inert gas；Carrier gas flux is 10 ml/mins~2000 ml/mins, preferred scope
For 500 ml/mins~1000 ml/mins.The number of plies of graphene can pass through carbon source concentration, growth time and alloy
The access times of substrate control.CVD growth temperature is 900 DEG C~1300 DEG C, and preferred scope is 950 DEG C~1050 DEG C；Growth
Time is 1 minute~300 minutes, preferably 10 minutes~50 minutes, preferably 15 minutes~45 minutes；Liter in heating process
Warm speed is 5 DEG C/min~100 DEG C/min, and preferred scope is 30 DEG C/min~50 DEG C/min.After growth, with 5 DEG C/
After minute~100 DEG C/min (preferred scope is 5 DEG C/min~30 DEG C/min) is slow cooling to 500 DEG C, with 100~300
DEG C/min fast cooling.The effect of above-mentioned heating mode is: high temperature needed for making reaction temperature be rapidly achieved experiment makes carbon source
Cracking reaction occurs, shortens experimental period, the effect of above-mentioned cooling method is: growth substrate has foot during slow cooling
The carbon source of dissolution is precipitated in the enough time, conducive to the formation of uniform number of plies graphene film.Temperature is reduced to carbon source Precipitation Temperature
When following, substrate is quickly cooled down and is taken out to shorten experimental period, and will not influence the uniformity of graphene film.
(2) coating of high molecular polymer protective layer: the uniform number of plies of high quality graphene film uniformly
One layer of high molecular polymer is coated as protective layer, to prevent graphene film from destroying in subsequent processes；
Graphene film is protected using one or more kinds of high molecular polymers, it is uniform convenient for the high quality number of plies
Graphene film transfer.These high molecular polymers are polymethyl methacrylate, polyethylene, polystyrene, polypropylene
One or more.
(3) it is bubbled transfer method: graphene film is transferred to other substrates from alloy substrates；Common metal etch
For method since metallic substrates to be lost make increased costs, the method for being bubbled transfer is being electrolysed metallic substrates and graphene
It is separated in liquid, obtaining high molecular polymer/graphene film composite membrane and metallic substrates, it can be used repeatedly.It is bubbled transfer
Electrolyte was sodium hydrate aqueous solution, potassium hydroxide aqueous solution.The electric current for being bubbled transfer is 0.1A~5A, preferably
0.2A~2A.
(4) removal of high molecular polymer protective layer: obtained high molecular polymer/graphene film composite membrane is placed
In target substrate, the high molecular polymer protective film dissolution removal on graphene film surface will be covered on organic solvent.
High molecular polymer protective layer is removed using organic solvent, the organic solvent used is acetone, ethyl lactate, dichloro
The one or more of the ketones such as ethane, trichloro ethylene, chloroform, halogenated hydrocarbons, aromatic hydrocarbons reagent.
The uniform number of plies graphene film of the high quality that the present invention obtains, the number of plies are 3~10 layers (preferably 3~6 layers), size
Depending on matrix size used in growth course, entire material composition is uniform, thickness is controllable, and light transmittance reaches as high as
93%, square resistance is the Ω of 10 Ω~1000 (the preferably Ω of 100 Ω~500).
The present invention is described in further detail below by embodiment and attached drawing.
Embodiment 1
Firstly, as shown in Figure 1, the present invention uses horizontal reacting furnace growing large-area high quality uniformly a small number of layer graphenes
Film, horizontal reacting furnace both ends are respectively equipped with gas access 1 and gas vent 3, and corronil substrate is placed in horizontal reaction
Corronil piece (125 microns of 10 cm x, 12 cm x, purity 99.8wt%, nickel content 30wt%) is put in furnace high-temperature region
It is placed in horizontal reacting furnace (70 millimeters of boiler tube diameter, react 10 centimetres of section length) middle section；In hydrogen and argon atmosphere
Being heated to 1000 DEG C, (hydrogen flowing quantity is 500 ml/mins in heating process, and argon flow is 500 ml/mins, heating rate
It is 25 DEG C/min), 90 minutes are kept the temperature after furnace temperature rises to 1000 DEG C, and corronil is made annealing treatment.After be passed through methane, hydrogen
Gas, argon gas mixed gas (gas flow rate is respectively 6.5 ml/min of methane, 500 ml/min of hydrogen, 500 milli of argon gas
Liter/min), start to grow different layers of graphene films, growth time is 50 minutes.With 30 DEG C/min after growth
It is slow cooling to after 500 DEG C with 200 DEG C/min of fast coolings, obtains the graphite of uniformly a small number of layers in corronil substrate surface
Alkene film.
Then, by the ethyl lactate solution of polymethyl methacrylate (PMMA) (polymethyl methacrylate accounts for 4wt%)
The corronil surface that growth has graphene film is dripped to, one layer of PMMA film is painted with 2000 revs/min of spin coating instrument, 130
It is put into 0.1mol/L sodium hydrate aqueous solution after being dried 15 minutes at a temperature of DEG C, electrochemistry bubbling is carried out under 0.5A electric current and is turned
It moves, PMMA/ graphene film is transferred to SiO2In/Si substrate or flexible PET base, then at 50 °C with acetone
PMMA is dissolved, the final successful transfer for realizing graphene film.
In the present embodiment, the uniform number of plies graphene film number of plies is 5 layers, every layer of graphene film with a thickness of 0.35nm.
Table is carried out using optical microscopy, scanning electron microscope and Raman spectrum pattern, crystalline quality and the number of plies to graphene
Sign shows to obtain uniform five layers of graphite film, multilayer or the region without growing graphene is not present in film.And film
Defect is less, and crystalline quality is very high.Film can completely be transferred to the test that photoelectric properties are carried out in PET base.
Embodiment 2
Firstly, as shown in Figure 1, the present invention uses horizontal reacting furnace growing large-area high quality uniformly a small number of layer graphenes
Film, horizontal reacting furnace both ends are respectively equipped with gas access 1 and gas vent 3, and corronil substrate is placed in horizontal reaction
Corronil piece (125 microns of 5 cm x, 6 cm x, purity 99.8wt%, nickel content 20wt%) is placed in furnace high-temperature region
In horizontal reacting furnace (70 millimeters of boiler tube diameter, react 10 centimetres of section length) middle section；Add in hydrogen and argon atmosphere
(hydrogen flowing quantity is 500 ml/mins to heat in heating process, and argon flow is 500 ml/mins, and heating rate is to 1000 DEG C
25 DEG C/min), 60 minutes are kept the temperature after furnace temperature rises to 1000 DEG C, and corronil is made annealing treatment.After be passed through methane, hydrogen
Gas, argon gas mixed gas (gas flow rate is respectively 7.0 ml/min of methane, 500 ml/min of hydrogen, 500 milli of argon gas
Liter/min), start to grow different layers of graphene films, growth time is 30~60 minutes.After growth with 30 DEG C/
Minute is slow cooling to after 500 DEG C with 200 DEG C/min of fast coolings, obtains uniform a small number of layers in corronil substrate surface
Graphene film.
Then, by the ethyl lactate solution of polymethyl methacrylate (PMMA) (polymethyl methacrylate accounts for 4wt%)
The corronil surface that growth has graphene film is dripped to, one layer of PMMA film is painted with 2000 revs/min of spin coating instrument, 130
It is put into 0.1mol/L sodium hydrate aqueous solution after being dried 15 minutes at a temperature of DEG C, electrochemistry bubbling is carried out under 0.5A electric current and is turned
It moves, PMMA/ graphene film is transferred to SiO2In/Si substrate or flexible PET base, then at 50 °C with acetone
PMMA is dissolved, the final successful transfer for realizing graphene film.
In the present embodiment, the uniform number of plies graphene film number of plies is 3~6 layers, every layer of graphene film with a thickness of
0.35nm.The pattern of different number of plies graphene films is characterized using optical microscopy, scanning electron microscope, is shown
The different layers of graphite film numbers of plies arrived are uniform, and there is no multilayer or the regions without growing graphene in film.And it is right
Different layers of graphene films carry out the test of photoelectric properties, show that the photoelectric properties of graphene film are excellent.
Embodiment 3
Firstly, as shown in Figure 1, the present invention uses horizontal reacting furnace growing large-area high quality uniformly a small number of layer graphenes
Film, horizontal reacting furnace both ends are respectively equipped with gas access 1 and gas vent 3, and corronil substrate is placed in horizontal reaction
Corronil piece (125 microns of 5 cm x, 6 cm x, purity 99.8wt%, nickel content 30wt%) is placed in furnace high-temperature region
In horizontal reacting furnace (70 millimeters of boiler tube diameter, react 10 centimetres of section length) middle section；Add in hydrogen and argon atmosphere
(hydrogen flowing quantity is 500 ml/mins to heat in heating process, and argon flow is 500 ml/mins, and heating rate is to 1000 DEG C
25 DEG C/min), 60 minutes are kept the temperature after furnace temperature rises to 1000 DEG C, and corronil is made annealing treatment.After be passed through methane, hydrogen
Gas, argon gas mixed gas (gas flow rate is respectively 7.0 ml/min of methane, 500 ml/min of hydrogen, 500 milli of argon gas
Liter/min), start to grow different layers of graphene films, growth time is 40 minutes.With 30 DEG C/min after growth
It is slow cooling to after 500 DEG C with 200 DEG C/min of fast coolings, obtains the graphite of uniformly a small number of layers in corronil substrate surface
Alkene film.
Then, by the ethyl lactate solution of polymethyl methacrylate (PMMA) (polymethyl methacrylate accounts for 4wt%)
The corronil surface that growth has graphene film is dripped to, one layer of PMMA film is painted with 2000 revs/min of spin coating instrument, 130
It is put into 0.1mol/L sodium hydrate aqueous solution after being dried 15 minutes at a temperature of DEG C, electrochemistry bubbling is carried out under 0.5A electric current and is turned
It moves, PMMA/ graphene film is transferred to SiO2In/Si substrate or flexible PET base, then at 50 °C with acetone
PMMA is dissolved, the final successful transfer for realizing graphene film.
In the present embodiment, the uniform number of plies graphene film number of plies is 3~6 layers, every layer of graphene film with a thickness of
0.35nm.The step that will be placed on a piece of corronil substrate more than after ultrasonic cleaning, being repeated in alcohol and acetone.Again
Obtain the graphene film of identical pattern.
The graphene film for using the substrate grown of different numbers to go out is subjected to morphology characterization using optical microscopy, is shown
Copper crosses the graphene film that the method for being bubbled transfer is used repeatedly corronil substrate, and obtains can be with retaining layer
Number uniformity.
As shown in Figure 1, CVD method of the present invention prepares the experimental provision of the uniform a small number of layer graphene film of large-area high-quality,
Specifically include that gas access 1, metallic substrates 2, gas vent 3, heating furnace 4, gaseous carbon source and carrier gas from gas access 1 into
Enter in the pipe of heating furnace 4 (solid-state carbon source can directly be coated or deposited on 2 upper surface of metallic substrates), be discharged from gas vent 3,
Metallic substrates 2 are corronil.
As shown in Fig. 2, different layers of uniform graphene films that the CVD method obtains, optics and scanning electron microscope
Photo shows that the material surface structural integrity, the number of plies are uniform.
As shown in figure 3, can be seen that five layers of graphene film of large area from Raman spectrum has good crystalline quality,
Defect is very low, and sample uniformity.
As shown in figure 4, the large-area graphene film that the CVD method obtains, can completely be transferred in PET base.
As shown in figure 5, the CVD method prepare the uniform graphene film of different layers of large-area high-qualities light transmittance
With the relationship of resistivity and the number of plies, it can be seen that different layers of uniform graphene films all have excellent optically and electrically property
Energy.
As shown in fig. 6, substrate can be used repeatedly after being shifted with Bubbling method, and all using the same substrate of different numbers
Uniform graphene film can be grown.
The above results show the advantages of graphene is grown on present invention combination copper and mickel, realize large area with corronil
The preparation of the uniform a small number of layer graphene film of high quality can be such that alloy substrates are used repeatedly in conjunction with the method for being bubbled transfer,
The features such as simple with preparation process, at low cost, the product number of plies and size are easy to regulate and control, and can be used for large area production.It is this big
Area and high quality minority layer graphene film have very high crystalline quality, the uniform number of plies, excellent visible light permeability, compared with
Low resistance value.This series structure performance characteristics is large-area high-quality uniformly a small number of layer graphene film scene effect crystal
The research and application in the fields such as pipe, transparent conductive film, flexible photoelectric device lay the foundation.
Claims (10)
1. a kind of method for preparing the uniform a small number of layer graphene film of large-area high-quality, which is characterized in that use corronil
As growth substrate, the graphene film of the uniform number of plies of large-area high-quality is prepared by chemical vapour deposition technique, it is subsequent
High quality uniformly a small number of layer graphene films are obtained with the method for being bubbled transfer.
2. the method described in accordance with the claim 1 for preparing the uniform a small number of layer graphene film of large-area high-quality, feature exist
In, the specific steps are as follows:
(1) the growth preparation of the uniform a small number of layer graphene film of large-area high-quality: in chemical vapor deposition processes, with cupro-nickel
Alloy is as growth substrate, and in conjunction with the advantage of two kinds of metal growth graphenes of copper and mickel, and then it is equal to prepare large-area high-quality
Even minority layer graphene film；
(2) coating of high molecular polymer protective layer: in the uniformly coating of the graphene film of the uniform number of plies of high quality
One layer of high molecular polymer prevents graphene film from destroying in subsequent processes as protective layer；
(3) it is bubbled transfer method: graphene film is transferred to other substrates from corronil substrate, using the side for being bubbled transfer
Method separates corronil substrate in the electrolytic solution with graphene, obtains high molecular polymer/graphene film composite membrane
And corronil substrate Reusability；
(4) obtained high molecular polymer/graphene film composite membrane the removal of high molecular polymer protective layer: is placed on mesh
It marks on matrix, the high molecular polymer protective film dissolution removal on graphene film surface will be covered on organic solvent.
3. the method according to claim 1 or 2 for preparing the uniform a small number of layer graphene film of large-area high-quality, feature
It is, for the corronil substrate thickness used for 1 μm~200 μm, purity is 98wt%~99.9999wt%, nickel in alloy
Content is 1wt%~50wt%.
4. the method according to claim 1 or 2 for preparing the uniform a small number of layer graphene film of large-area high-quality, feature
It is, during chemical vapour deposition reaction, carbon source is hydrocarbon: methane, ethane, ethylene, acetylene, benzene, toluene, hexamethylene
The one or more of alkane, ethyl alcohol, methanol, acetone, carbon monoxide；Alternatively, carbon source be solid carbon source: amorphous carbon, paraffin,
The one or more of high molecular polymer, high molecular polymer are polymethyl methacrylate, polycarbonate, polyphenyl second
The one or more of alkene, polyethylene, polypropylene.
5. the method according to claim 1 or 2 for preparing the uniform a small number of layer graphene film of large-area high-quality, feature
It is, during chemical vapour deposition reaction, carrier gas is hydrogen or carrier gas is the mixed gas of hydrogen and inert gas.
6. the method according to claim 1 or 2 for preparing the uniform a small number of layer graphene film of large-area high-quality, feature
It is, the temperature of chemical vapor deposition growth graphene is 900 DEG C~1300 DEG C, and growth time is 1~300 minute.
7. the method according to claim 1 or 2 for preparing the uniform a small number of layer graphene film of large-area high-quality, feature
It is, the electrolyte for being bubbled transfer was sodium hydrate aqueous solution or potassium hydroxide aqueous solution, and the electric current for being bubbled transfer is
0.1A~5A.
8. the method for preparing the uniform a small number of layer graphene film of large-area high-quality according to claim 2, feature exist
In protective layer using high molecular polymer as the uniform a small number of layer graphene film of high quality, so that graphene film be turned
Move on on other matrixes, high molecular polymer be polymethyl methacrylate, polyethylene, polystyrene, polypropylene one kind or
It is two or more.
9. the method for preparing the uniform a small number of layer graphene film of large-area high-quality according to claim 2, feature exist
In, after graphene is separated with corronil substrate, with organic solvent remove high molecular polymer protective layer, use it is organic molten
Agent is the one or more of ketone, halogenated hydrocarbons, aromatic hydrocarbons reagent.
10. the method according to claim 1 or 2 for preparing the uniform a small number of layer graphene film of large-area high-quality, special
Sign is, the uniform number of plies graphene film number of plies is 3~10 layers, every layer of graphene film with a thickness of 0.3~0.8nm, the number of plies
Depending on the access times of the supply of carbon source amount, growth time and corronil substrate, size depends on institute in preparation process
The size of the metallic matrix used, entire material composition is uniform, thickness is controllable, and light transmittance is 85% or more, square resistance 10
The Ω of Ω~1000.
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